Herbicidal composition and method of using 4-alkyl-amino-3-nitroquinolines

ABSTRACT

WHEREIN: R1 and R2 are each hydrogen, lower alkyl, or (lower alkylthio)lower alkyl except that R1 and R2 may not both be hydrogen, X is halo, nitro, or trifluoro(lower)alkyl, and n is 0 to 3.   The herbicidal compounds have the formula:

United States Patent [191 Diehl et al.

[111 3,837,836 1' Sept. 24, 1974 [75] Inventors: Robert Eugene Diehl,Trenton;

Richard Joseph Magee, Princeton, both of NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

22 Filed: May 26,1972

21 App]. No.: 257,464

Related US. Application Data [62] Division of Ser. No. 820,649, April30, 1969, Pat.

[52] US. Cl. 71/94 [51] Int. Cl A0111 9/22 [58] Field of Search 71/94[56] References Cited UNITED STATES PATENTS 2,066,730 l/1937 Jensch260/288 X 3,113,072 12/1963 Goodhue et al. 260/288 3,252,858 5/1966Goodhue et al.. 260/283 X 3,538,099 11/1970 Rohr et al..... 71/94 X3,547,935 12/1970 Diehl et al. 71/94 OTHER PUBLICATIONS Sunney et al.,Jour. Am. Chem. Soc., Vol. 73, pgs. 24132416, 1951.

Jain et al., Chem. Abstr., V01. 68, C01. 11439 (t),

Primary Examiner-James 0. Thomas, Jr Attorney, Agent, or Firm1-l. G.Jackson ABSTRACT The herbicidal compounds have the formula:

X is halo, nitro, or trifluoro(1ower)alkyl, and n is 0 to 3.

wherein:

9 Claims, N0 Drawings HERBICIDAL COMPOSITION AND METHOD OF USING4-ALKYL-AMINO-3-NITROQUINOLINES This is a division, of application Ser.No. 820,649. filed Apr. 30, 1969 now US. Pat. No. 3,700,674 (1972).

SUMMARY OF THE INVENTION This invention relates to novel herbicidal 4-alkylamino-3-nitroquinolines represented by the formula:

wherein:

R and R are each selected from the group consisting of hydrogen, loweralkyl, and (lower alkylthio) lower alkyl provided that when either R, orR is hydrogen, the other must be lower alkyl or (lower alkylthio) loweralkyl,

X is selected from the group consisting of halo, nitro, andtrifluoro(lower)alkyl, and

' n is O to 3.

This invention also relates to the acid salts of said compounds and inparticular to the strong mineral acid salts thereof such as, forexample, those of hydrochloric and hydrobromic acid.

This invention further relates to the use of said compounds and theiracid salts as pre-emergence and post emergence herbicides.

The term lower alkyl when used alone means straight and branchedsaturated hydrocarbon chains containing from one to five carbon atoms.Illustrative members are methyl, ethyl, n-propyl, n-pentyl, n-butyl,isopropyl, Z-butyl, 3-butyl, 2-pentyl, 3-pentyl, and such.

The term lower alkyl" when used in conjunction with thio radicals suchas (lower alkylthio) lower alkyl radicals means only saturatedhydrocarbon chains containing one or two carbon atoms such as(methylthio) methyl, (methylthio) ethyl, (ethylthio) methyl, and(ethylthio) ethyl.

The term halo means chloro, bromo, iodo, and fluoro.

The following compounds are illustrative of the compounds of thisinvention. These compounds are named in accordance with the numbering ofthe quinoline ring given in the preceding formula:

4-methylamino-3-nitroquinoline 4-ethylamino-3-nitroquinoline4-n-propylamino-3-nitroquinoline 4-n-butylamino-3-nitroquinoline4-n-pentylamino-3-nitroquinoline 4-(i-propyl)amino-3-nitroquinoline4-(2-butyl)amino-3-nitroquinoline 4-dimethylamino-3-nitroquinoline4-diethylamino-3-nitroquinoline 4-dipropylamino-3-nitroquinoline4-di(i-propyl)amino-3-nitroquinoline 4-di(n-butyl)amino-3-nitroquinoline2 4-di(n-pentyl)amino-3-nitroquinoline4-di(2-butyl)amino-3-nitroquinoline4-methyl(ethyl)amino-3-nitroquinoline 4-methyl( n-propyl)amino-3-nitroquinoline 4-ethyl(n-butyl)amino-3-nitroquinoline4-n-butyl(i-propyl)amino-3-nitroquinoline 4-n-pentyl( Z-butyl)amino-3-nitroquinoline 4-n-propyl(ethyl )amino-3-nitroquinoline6,7,8-trifluoro-4 methylamino-3-nitroquinoline6,7,8-trichloro-4-n-propylamino-3-nitroquinoline6,7,8-tri(trifluoromethyl )-4-n-butylamino-3- nitroquinoline6,7,8-triiodo 4-n-pentylamino-3-nitroquinoline 5,6,7-trichloro-4-(i-propyl )amino-3-nitroquinoline 5,6,7-tribromo-4-(2-butyl )amino-3-nitroquinoline 5,6,8-trichloro-4-dimethylamino-3-nitroquinoline 5,7,8-tribromo-4-diethylamino-3nitroquinoline8-chloro-7-bromo-6-fluoro-4-dipropylamino-3- nitroquinoline7,8-dichloro-6-iodo-4-di( i-propyl)amino-3- nitroquinoline6,7-dibromo-8-chloro4-di(n-butyl )amino-3- nitroquinoline5,6-dichloro-7-bromo-4-di(n-pentyl )amino-3- nitroquinoline5,8-dichloro-4-di( 2-butyl )amino-3-nitroquinoline6,7-dichloro-4-methyl(ethyl )amino-3-nitroquinoline5,6dichloro-4-methyl(n-propyl)amino-3- nitroquinoline7,8-dibromo-4-ethyl(n-butyl )amino-3-nitroquinoline 5,6-diiodo-4-n-butyl( i-propyl)amino-3- nitroquinoline6,7-difluoro-4-n-pentyl( 2-butyl)amino-3- nitroquinoline8-chloro-4-n-propyl(ethyl)amino-3-nitroquinoline7-trifluoromethyl-4-methylamino-3-nitroquinoline6-iodo-4-n-propylamino-3-nitroquinoline5-fluoro-4n-butylamino-3-nitroquinoline 6chloro-4-n-pentylamino-3-nitroquinoline8-nitro-4-(i-propyl)amino-3-r1itr0quinoline 7-nitro-4-( 2-butyl)amino-3-nitroquinoline 6-nitro-4-dimethylamino-3 nitroquinoline5-nitro-4-diethylamino-3-nitroquinoline 8-trifluoromethyl-7-chloro-4dipropylamino-3- nitroquinoline 8-bromo-6-nitro-4-di(i-propyl)amino-3-nitroquinoline 7,8-dichloro-5-nitro-4-di(n-pentyl)amino-3-nitroquinoline 6,7-dinitro-8-chloro-4-methyl(ethyl)amino-3-nitroquinoline 6,7,8-trinitro-4-ethyl(n-butyl)amino-3- nitroquinoline 5,6,7-trinitro-4-n-butyl( i-propyl )amino-3- nitroquinoline6,7-dinitro-4-n-pentyl( 2-butyl )amino-3 nitroquinoline 5,6-dinitro-4-n-propyl(ethyl )amino-3-nitroquinoline Process ofPreparation The compounds of this invention are conveniently prepared byreacting the appropriately substituted 4- chloro(orbromo)-3-nitroquinoline with the appropriate alkyl amino preferably in asuitable solvent in accordance with the reaction shown below:

excess of the amine, usually at least about 2 moles of amine per mole of3-nitroquinoline compound. The excess amine forms an acid salt whichprecipitates from the reaction mixture thereby aiding purification ofthe desired product. After the precipitated acid salts are separatedfrom the reaction mixture, solvent is removed to yield a crude productwhich can be subsequently purified by recrystallization in acetone orother suitable solvents. Of course, if the acid salt of an inventivecompound is desired, it is a simple matter to merely react the productwith the desired acid in a manner which is well known. StartingMaterials The vast majority of the reactant amines are readily availableon a commercial basis. Techniques for pre paring the other aminesrequired are either well known or obvious to those skilled in the art soas to not require repeating herein.

Reactant 4-chloro-3-nitroquinolines of the formula:

wherein X is halo, nitro or trifluoro(lower)alkyl and n is O to 3 areconveniently prepared by a variety of methods depending on suchconsiderations as the availability of the starting material andelectronic requirements of the reaction.

Thus, various appropriately substituted 4-chloro-3- nitroquinolines canbe prepared from commercially available anthranilic acids in accordancewith the teachings of Bachman, et al., J.A.C.S. 69 pages 365-370 (1947),said publication incorporated herein by reference.

Altematively, the desired reactants are conveniently prepared by thedecarboxylation of commercially avail able compounds of the formula:

| A coon wherein X and n are as defined above, in accordance with theteaching in J.A.C.S. 69 page 371, said publication incorporated hereinby reference. The decarboxyl ated product is then nitrated in aconventional manner to insert 2 nitro group into the number 3 positionof the quinoline ring. The nitrated quinoline is then treated inaccordance with the process of Bachman, et al., cited above, to yieldthe desired 3-nitro-4-chloroquinoline reactant.

The desired reactant can also be prepared by reacting ethyl oxalacetateand an aromatic amine as described in US. Pat. No. 2,555,943 to obtain a2- carboethoxy derivative of the formula:

wherein X and n are as defined above. This compound is then hydrolyzedand decarboxylated as described in said patent. The product is thentreated with nitric acid and finally converted to the 4-chloroderivative by the process of Bachman, et al., cited above.

Utility The compounds of this invention exhibit preemergence herbicidalactivity towards a variety of broad and narrow leaf plant species.Pre-emergence control is particularly effective as amply demonstrated bythe data of Example 14 hereinbelow. It should be noted that thepre-emergence herbicidal activity of these compounds is highly selectiveinsofar as they are effective against a broad range of undesirable weedswhich grow among crops while simulaneously having no discernibleherbicidal effect upon such useful economic crops as corn, cotton.radish, sugar beets, soybeans, and wheat.

Certain selected compounds of this invention exhibit post emergenceherbicidal activity towards a variety of broad and narrow leaf plantspecies as amply demonstrated by the data of Example 15. While all ofthe inventive compounds exhibit pre-emergence herbicidal activity, onlythose compounds where n is zero and R, and R are each lower alkyl or(lower alkylthio) lower alkyl appear to exhibit any significant postemergence herbicidal activity. Post emergence control is also highlyselective in that crops such as tomatoes and wheat are left virtuallyunharmed while the harmful weeds and grasses which grow among such cropsare effectively destroyed.

Application of the compounds of the invention for purposes of herbicidalcontrol can be accomplished employing both conventional type formulationand equipment. The compounds may, for instance, be formulated aswettable powders, dusts, dust concentrates, emulsifiable concentratesand the like which are amenable to application with conventionalspraying or dusting apparatus.

Wettable powder formulations are generally prepared by admixing fromabout 25 percent to about percent, by weight, of active ingredient withfinely ground clay, such as kaolin or attapulgite, either with orwithout a surface active agent, emulsifier or spreader-sticker. Thelatter is then dispersed in water for spray application.

Dusts and dust concentrates are similarly prepared using from about 5percent to about 95 percent of active ingredient and from about 95percent to about 5 percent of finely divided inert ingredients. Thesedusts are generally applied as such, or they may be further diluted withfinely ground inert solids and then applied with conventional dustingapparatus.

Emulsifiable concentrates may be prepared by dissolving or dispersingthe active ingredient in organic EXAMPLE 12 Preparation of5,8-dichloro-3,6-dinitro-4-di-npropylaminoquinoline solvent, with orwithout emulsifying agents, surfactants 5 c1 N(CaH7-u)l or the like.Such formulations are then diluted with e1- 1 I ther water or anappropriate organic diluent prior to o, application.

The following examples are provided to further illustrate the invention.J;

EXAMPLE 1 I P f 4 1 3 5.0 Grams of 5,8-dichloro4-hydroxyquinoline[Preepara O ammo me pared according [0 us. 2,555,943 (CA. 45, 9568)] isadded to a solution of nitric acid (50 ml.) and sulfuric N(C;H1-ii)2acid 50 ml.) at 2545o The resulting mixture is A I heated for 2 to 4hours at 8090C. and poured into NO1' 500 ml. of ice-water. Theprecipitated solid is filtered n and washed well with water. The sampleis recrystallized from dimethylformamide-water to give 5,8-

dichloro-3,6-dinitro-4-hydroxyquinoline. The product I i is thenconverted to 4,5,8-trichloro-3,6- The mle COmPOund lS Prepared byrefluxmg Sample dinitroquinoline following the method of Bachman, et of4-chloro-3-n1troqu1nol1ne (4.16 g., 0.02 mole) and a1 69, pages 365 37O(1947). di-n-propylamme -1 -9 molelm 40 of I019- The desired product,5,8-dichloro-3,6-dinitro-4-di-nene for 2 hours. The mixture is thenfiltered to remove propylaminoquinoline, is then prepared following theinsoluble hydrochlor de salts. The filtrate is constamiany the Sameprocedure as in Example 1 except centratedi Y to weld 8 Percent) of athat the 4-chloro-3-nitroquinoline is replaced by 4,5,8- dark brown oilwhich gradually crystallizes. After three i l 3 6 i i i irecrystallizations from acetone, the yellow-orange solid has a meltingpoint of 6364C. Calculated for EXAMPLE 13 C15H19N302: r H, i Foundi C!Preparation of 5,8-dibromo-3,6-dinitro-4-di-n- 66-12propylaminoquinoline EXAMPLES 2 TO 11 ITHCJHH), A variety of otherinventive compounds were pre- 35 pared substantially as described inExample 1 except that the appropriate 4-chloro-3-nitroquinoline andamine reactants were selected. These compounds and I N certain of theirproperties are shown below in Table 1. Br

TABLE I R1\ /Rz l NOz fi/% NO2 XL7- 9 RiRiNii X% 0 +1101 Example MeltingNumber R R2 R; X Point(C) C h N S Cl F 2 H CH(CH;,): H H 98 c-' 65.907.00 15.37 f 66.12 6.93 15.09 3 CH, noH, H H 72-73 c 65.91 7.00 15.37 f65.63 7.09 15.25 4 n-C H nC -;H H CH6) 93-94 0 58.53 5.89 13.65 11.52 f58.44 6.00 13.48 11.61 5 ri-C H ri-c H, H C1171 74-75 c 58.53 5.89 13.6511.52 f 58.86 6.03 13.80 11.55 6 l'l-c H- n-C;;H; H Cl(8) -106 c 58.535.89 13.65 11.52 f 58.72 5.79 13.74 11.70 7 CH ri-C.H H c117) 63-64 c58.53 5.89 13.65 11.52 f 58.49 5.78 13.54 11.26 3 W H, n c,,H, H 1 0 7)94-95 c 56.30 5.31 12.31 16.70 f 5664 5.25 12.39 16.88 9 ll-C H; n-c llH F3C(8) 116-118 c 56.30 5.31 12.31 16.70 f 56.23 5.02 12.08 16.91 10n-CiH ri-QH, H 610 6) 101-102 c 56.59 5.69 1760 f 56.54 5.64 17.50 11ii( .H, CH CH- r-S-(H;, H H 69-71 58.99 6.27 13.75 10.50 f 5925 6.4213.78 10.49

' nuinliur in parenthesis ll\\llLi\lL\ ring position i--- calculated jl'uuml The above compound is prepared following substan- 8 85 100 nt r dti i t d tially the same procedure as in Example 12 except that 7 70 85percent reduction in stand 5,8-dichloro-4-hydroxyquinoline is replacedby 5,8- 6 60 70 percent reduction in stand dibromo-4-hydroxyquinoline.50 60 percent reduction in stand 5 4 40 50 percent reduction in standEXAMPLE 3 30 40 percent reduction in stand Pre-Emergence Herbi i 2 20 30percent reduction in stand The pre-emergence herbicidal activity of thecom- 1 20 Peircet reduction m Stand pounds of the invention isexemplified by the following 0 no apparent effect tests in which theseeds of various monocotyledonous 10 a abnormal, m twisted anddicotylendonous plants are separately mixed with 8 unusualphl'slologlcal effect potting soil and planted on top of approximatelyone m 2 fi t mlury inch of potting soil in separate pint cups. Afterplants 2 Severe f 4 ing, the cups are sprayed with the selected aqueoustitrace to Shght l acetone solution containing the test compound insuffil 4 cient quantity to provide the equivalent in pounds perAbbrevlanons for the Plant Specles employed acre of test compound percup. The treated cups are amples 14 and 15 are as follows:

then placed on greenhouse benches and cared for in the usual manner, inaccordance with greenhouse procedures. Two weeks after treatemnt, thetests are ter- 3;, Barnyard Grass Mu Mustard minated and each cup isexamined and rated according Com N Cot Cotton Ra Radish to the definedHerbitoxicity Index given in the table be- CT grabgmss I 53 Sugar hemlow. The tabulated results of these tests are shown E E i i y am 5 U3!['5 O omatoes below in Table II, and establish the herbicidal profi- Mmeq e W0 Om clency of the test compounds. WH Wheat TABLE II PRBEM ERGENCEHERBICIDAL DATA Compound of Example Number LbJAcre Pi Ba Cr GRF WO MiCor Cot Ra SB Soy WH 5 7ga 8a 9a 9a ta l 10 9 9a 9 9a 6a 3 tga 7 3a 7 OO 0 O U W 3 9 sgu 8a 9 O O 0 O O 5 5g 8n 9 9a 0 4 15 5g 95 9 9 0 25 9a OU 5 O mga 4 sga O w v 5 15 5g 95 7 9 0 4 3a 95 9K 0 O O 0 0 0 TABLE IllPOST EMERGENCE HERBICIDAL DATA Compound of Example Number Lb.fAcre Ln MuPi Ba Cr GRF TO WH 1 l0 9 ma 9 in 8a ma sa 0 65 Herbitoxicny Index Iclaim:

9 percent reduction in stand I. A herbicidal composition comprising 9 lor 2 Stunted plants remaining a herbicidally effective amount of acompound of l NO: X l J 3. A method for controlling undesirable plantspecies which comprises applying to the soil containing seeds of saidundesirable plant species a herbicidally effective amount of a compoundof the formula I A N02 wherein R and R are hydrogen, lower alkyl C -C or(lower alkylthio C -C lower alkyl C -C provided that when either R or Ris hydrogen the other must be lower alkyl or (lower alkylthio) loweralkyl,

X is halo, trifluoromethyl or hydrogen.

4. A method for controlling undesirable plant species which comprisesapplying to the foliage of said undesirable plant species a herbicidallyeffective amount of a compound of the formula wherein R and R arehydrogen, lower alkyl C -C or (lower alkylthio C -C lower alkyl C -Cprovided that when either R or R is hydrogen the other must be loweralkyl or (lower alkylthio) lower alkyl,

X is halo, trifluoromethyl or hydrogen.

5. The method of claim 3 wherein said soil also contains the seeds ofeconomic crops.

6. The method for controlling undesirable plant species according toclaim 3 wherein R and R are each lower alkyl C -C 7. A method forcontrolling undesirable plant species according to claim 6 wherein thecompound is 8. A method for controlling undesirable plants according toclaim 4 wherein R and R are each lower alkyl C,-C

9. A method for controlling undesirable plants according to claim 8wherein the compound is UNITED STATES mTgENT OFFKCE TWNATE p Patent NO.3,837,836 Date September 24, 1914 l i ROBERT EUGENE DIEHL AND RICHARDJOSEPH MAGEE It is certified that error appears in the above-identifiedpatent and that said'Letters Patent are hereby corrected as shown below:

Column 3, Line 613, c'ieiete the formula and replace with the fallowingformula:

Signed an sealed this 25th day of November 1974.

w (QEAL) MQCQY Mg JR, C E'LKRSMLL DANE PC4050 0&9, uscoMM-nc scan-pee

2. The composition of claim 1 wherein the compound is:
 3. A method forcontrolling undesirable plant species which comprises applying to thesoil containing seeds of said undesirable plant species a herbicidallyeffective amount of a compound of the formula
 4. A method forcontrolling undesirable plant species which comprises applying to thefoliage of said undesirable plant species a herbicidally effectiveamount of a compound of the formula
 5. The method of claim 3 whereinsaid soil also contains the seeds of economic crops.
 6. The method forcontrolling undesirable plant species according to claim 3 wherein R1and R2 are each lower alkyl C1-C5.
 7. A method for controllingundesirable plant species according to claim 6 wherein the compound is8. A method for controlling undesirable pLants according to claim 4wherein R1 and R2 are each lower alkyl C1-C5.
 9. A method forcontrolling undesirable plants according to claim 8 wherein the compoundis